CN105728052A - Method for preparing high-photo catalytic active nanometer titania by using waste wool - Google Patents
Method for preparing high-photo catalytic active nanometer titania by using waste wool Download PDFInfo
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- CN105728052A CN105728052A CN201610055563.XA CN201610055563A CN105728052A CN 105728052 A CN105728052 A CN 105728052A CN 201610055563 A CN201610055563 A CN 201610055563A CN 105728052 A CN105728052 A CN 105728052A
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- Prior art keywords
- caprae seu
- seu ovis
- pilus caprae
- old
- titanium dioxide
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 80
- 210000002268 wool Anatomy 0.000 title abstract description 10
- 239000000835 fiber Substances 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 97
- 241000283898 Ovis Species 0.000 claims description 93
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 79
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 39
- 229960004756 ethanol Drugs 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 28
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 239000004115 Sodium Silicate Substances 0.000 claims description 13
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 13
- 150000003608 titanium Chemical class 0.000 claims description 13
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 13
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 238000005520 cutting process Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 235000015598 salt intake Nutrition 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 150000001413 amino acids Chemical class 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 43
- 230000000052 comparative effect Effects 0.000 description 26
- 230000001699 photocatalysis Effects 0.000 description 16
- 230000004044 response Effects 0.000 description 11
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 11
- 229940043267 rhodamine b Drugs 0.000 description 11
- 230000003750 conditioning effect Effects 0.000 description 10
- 238000002791 soaking Methods 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229960003067 cystine Drugs 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 241000345998 Calamus manan Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- -1 amino acids small-molecule Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000002228 disulfide group Chemical group 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing high-photo catalytic active nanometer titania by using waste wool. The method comprises the following steps: hydrolyzing wool under an acidity condition to generate amino acid small molecular substances, and performing doping modification on nanometer titania crystalline grains produced in the hydrothermal reaction process, covering a layer of organic substance film on the surface of the crystalline grains to prepare the nanometer titania with high-photo catalytic performance. Through the adoption of the hydrothermal method, the wool short fiber is added in the low-temperature hydrothermal and strong-acidity environment, in the growing process of the nanometer titania crystals, the wool fiber is synchronously hydrolyzed to generate the small molecular organic substances, thereby hybridizing the nanometer titania crystalline grains and performing the surface graft modification without adding other chemical reagents or surfactants; the preparation process is simple, the solution is neutral finally, and the emission cannot cause secondary pollution to the environment.
Description
Technical field
The invention belongs to Textile Engineering technical field, be specifically related to a kind of method utilizing waste and old Pilus Caprae seu Ovis to prepare highlight catalytic active nano titanium dioxide.
Background technology
The photocatalysis characteristic of titanium dioxide is since the 20 clear professors in century 70 Tokyo Univ Japan rattan island find first, owing to it has good double; two affinitys and sterilising, it is widely used at present in the industries such as anti-ultraviolet material, weaving, photocatalysis catalyst, glass with clean, sunscreen cream, coating, ink, packaging material for food, paper industry, aerospace industry, lithium battery.Hydrothermal Synthesis technology is used to prepare a kind of important method of nano-oxide, hydro-thermal method is possible not only to prepare the tiny crystals of some one pack systems, and bi-component or multi-component material can be prepared, overcome the unfavorable factors such as some unavoidable hard aggregation of hot conditions, research shows, the position of energy band of titanium dioxide and the reduction potential of adsorbed material determine the ability of its photocatalytic activity.
At present, people, based on hydro-thermal method, respectively with butyl titanate, isopropyl titanate, titanium sulfate, titanium tetrachloride etc. for presoma, have successfully prepared the nano titanium oxide of anatase or rutile-type；Or add metallic element (such as silver, ferrum, copper etc.), nonmetalloid (such as carbon, nitrogen, sulfur etc.), rare earth element (such as europium, neodymium, lanthanum etc.) to strengthen the photocatalytic activity of nano titanium oxide, improve the absorbability to visible ray.Pilus Caprae seu Ovis is mainly made up of keratin matter, and wherein protein content in angle accounts for 97%, and inorganic matter accounts for 1～3%.The essential element constituting angle protein includes carbon, oxygen, nitrogen, sulfur and hydrogen etc..Angle protein is to be made up of multiple a-amino acid residue, containing the groups such as carboxyl, amido and hydroxyl, intermolecular formation salt type bond and hydrogen bond etc. on its macromolecular chain, is connect by the disulfide bond of cystine between long-chain.Pilus Caprae seu Ovis is more acidproof but not alkaline-resisting, this is because alkali easily decomposes the disulfide group of cystine in Pilus Caprae seu Ovis.Until today, the recycling of waste and old Pilus Caprae seu Ovis is but without solving well.Pilus Caprae seu Ovis is utilized to be hydrolyzed in an acidic solution, generate the small-molecule substance rich in organic principle, prepare in nano titanium oxide process in butyl titanate (or isopropyl titanate, titanium sulfate, titanium tetrachloride) hydro-thermal reaction, the organic elements such as the carbon of Pilus Caprae seu Ovis hydrolysis generation, nitrogen, sulfur are entrained in titanium dioxide granule surface and form a thin clad, improve the nano titanium oxide photocatalytic activity to ultraviolet and visible ray.At present about using the correlation technique that waste and old Pilus Caprae seu Ovis prepares highlight catalytic active nano titanium dioxide have not been reported.
Summary of the invention
It is an object of the invention to provide a kind of method utilizing waste and old Pilus Caprae seu Ovis to prepare highlight catalytic active nano titanium dioxide, waste and old Pilus Caprae seu Ovis is hydrolyzed, make the organic elements such as carbon therein, nitrogen, sulfur be entrained in titanium dioxide granule surface and form a thin clad, improve the nano titanium oxide photocatalytic activity to ultraviolet and visible ray.
The technical solution adopted in the present invention is, a kind of method utilizing waste and old Pilus Caprae seu Ovis to prepare highlight catalytic active nano titanium dioxide, and concrete preparation process is:
Step 1, utilizes titanium salt to prepare precursor solution；
Step 2, waste and old Pilus Caprae seu Ovis pretreatment, obtain Pilus Caprae seu Ovis chopped fiber；
Step 3, utilizes the precursor solution of step 1 gained and step 2 gained Pilus Caprae seu Ovis chopped fiber to carry out the preparation of nano-titanium dioxide powder.
Inventive feature also resides in,
In step 1, the process for preparation of precursor solution is:
Weighing titanium salt, be dissolved in dehydrated alcohol, after stirring, be slowly added to deionized water, obtain white " milky " clear solution, recycling hydrochloric acid or sulphuric acid regulate its pH to 1～2, obtain precursor solution, standby.
Titanium salt is the one in butyl titanate, isopropyl titanate, titanium tetrachloride or titanium sulfate.
In gained precursor solution, titanium salt is 1:1 with the amount ratio of dehydrated alcohol；The consumption of deionized water is 7 times of titanium salt and dehydrated alcohol total amount.
In step 2, the detailed process of Pilus Caprae seu Ovis pretreatment is:
Step 2.1: weigh waste and old Pilus Caprae seu Ovis, it is placed in alkaline mixed solution immersion treatment 30～50min, then soak 10～20min with 30 DEG C～50 DEG C ethanol solutions, then by rinsed with deionized water 1～3 time, finally clean Pilus Caprae seu Ovis is dried under 80 DEG C～110 DEG C conditions；
Step 2.2: step 1.1 gained Pilus Caprae seu Ovis is cut into the length chopped fiber less than 5mm with rotating torsion blade fibre cutting machine.
In step 2.1, the pH of alkaline mixed solution is 8.5～9.5, and alkaline mixed solution is mixed by hydrogen peroxide, sodium carbonate and sodium silicate, wherein, and the hydrogen peroxide 10～20ml/L of mass concentration 30%, sodium carbonate 0.5g/L～2g/L, sodium silicate 0.5g/L～2g/L.
In step 2.1, the bath raio of waste and old Pilus Caprae seu Ovis and alkaline mixed solution is 1:30～50.
In step 3, the concrete preparation process of nano-titanium dioxide powder is:
Step 3.1: step 2 gained Pilus Caprae seu Ovis chopped fiber is immersed in step 1 gained precursor solution after 5～10min, it is transferred in high-temperature high-pressure reaction kettle, after sealing, high-temperature high-pressure reaction kettle is placed in homogeneous reactor, with 1 DEG C/min～3 DEG C/min ramp to 110 DEG C～130 DEG C, after 100～200 turns/min speed isothermal reaction 2h～5h, it is cooled to room temperature, is centrifuged processing；
Step 3.2: the supernatant after centrifugal is outwelled, residual liquid is immersed in acetone soln, ultrasonic cleaning 10～20min when frequency 40kHz, power 100W, then ultrasonic cleaning 10～20min in ethanol solution it is immersed in, followed by deionized water ultrasonic cleaning 3 times, each 5～10min, finally vacuum drying under 100 DEG C～120 DEG C conditions, after grinding, obtain nano-titanium dioxide powder.
In step 3.1, the consumption of Pilus Caprae seu Ovis chopped fiber is in precursor solution the 1～10% of titanium salt consumption.
The invention has the beneficial effects as follows,
(1) present invention adopts hydro-thermal method, with butyl titanate (or isopropyl titanate, titanium sulfate, titanium tetrachloride) for presoma, low-temperature hydrothermal, strong acidic environment add Pilus Caprae seu Ovis chopped fiber, nano titanium dioxide crystal is generating, in the process grown up, wool fiber synchronous hydrolysis generates micromolecular Organic substance, thus titania being carried out hydridization and surface graft modification, without adding other chemical reagent and surfactant, preparation technology is simple, solution is finally in neutrality, and environment will not be caused secondary pollution by emission.
(2) when the present invention uses butyl titanate, isopropyl titanate and titanium sulfate to be presoma, it is possible to prepare anatase-type nanometer titanium dioxide granule, and when to use titanium tetrachloride be presoma, it is possible to prepare rutile type nano titanic oxide.The nano titanium oxide of both crystal formations can be adulterated and surface graft modification by the small organic molecule that in course of reaction, Pilus Caprae seu Ovis hydrolysis generates, but will not destroy the crystal structure of titanium dioxide.The little molecular coil that wool fiber hydrolysis simultaneously generates can control titania size, it is possible to effectively prevents nano titanium oxide from producing to reunite.
(3) the nano titanium oxide not only photocatalytic activity of the doping organic element that the present invention prepares is strong, and long service life, can repeated multiple times use, even if the organic principle being coated on titanium dioxide granule surface is immersed in the organic solvent such as acetone, dehydrated alcohol without dissolving.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the embodiment of the present invention 3 gained nano titanium oxide；
Fig. 2 is the stereoscan photograph of the embodiment of the present invention 6 gained nano titanium oxide；
Fig. 3 is the energy spectrogram of the embodiment of the present invention 3 gained nano titanium oxide；
Fig. 4 is the energy spectrogram of the embodiment of the present invention 6 gained nano titanium oxide；
Fig. 5 is the X-ray diffraction spectrogram of the embodiment of the present invention 3, embodiment 6, comparative example 1 and comparative example 2 gained nano titanium oxide；
Fig. 6 is the UV-Vis reflective spectrum curve of the embodiment of the present invention 3, embodiment 6, comparative example 1 and comparative example 2 gained nano titanium oxide；
Fig. 7 is the ultraviolet irradiation photocatalytic degradation rhodamine B curve of the embodiment of the present invention 3, embodiment 6, comparative example 1 and comparative example 2 gained nano titanium oxide；
Fig. 8 is the visible light exposure photocatalytic degradation rhodamine B curve of the embodiment of the present invention 3, embodiment 6, comparative example 1 and comparative example 2 gained nano titanium oxide.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The present invention uses butyl titanate (or isopropyl titanate, titanium sulfate, titanium tetrachloride) preparation of nano TiO 2 precursor solution, then Pilus Caprae seu Ovis is made to occur hydrolysis to generate amino acids small-molecule substance in acid condition, the last nano titanium oxide crystal grain generated in hydrothermal reaction process carries out doping vario-property, one layer of organic substance thin film is wrapped up, to improve the photocatalysis performance of nano titanium oxide at grain surface.
A kind of method utilizing waste and old Pilus Caprae seu Ovis to prepare highlight catalytic active nano titanium dioxide of the present invention, becomes small-molecule substance by waste and old Pilus Caprae seu Ovis at acidic solution hydrolysis and nano titanium oxide crystal grain carries out doping parcel, and concrete preparation process is:
Step 1, preparation butyl titanate (or isopropyl titanate, titanium sulfate, titanium tetrachloride) precursor solution；
Measure butyl titanate (or isopropyl titanate, titanium sulfate and urea liquid, titanium tetrachloride) solution, then it is dissolved in ethanol solution, and constantly stir, it is subsequently added into deionized water, it is slowly added into while stirring rapidly, forming white " milky " clear solution, finally using hydrochloric acid (or sulphuric acid) to regulate mixed solution pH value is 1～2；Wherein, the amount ratio of butyl titanate (or isopropyl titanate, titanium sulfate, titanium tetrachloride) solution and dehydrated alcohol is 1:1, and the consumption of deionized water is 7 times of titanium salt and dehydrated alcohol total amount.
Step 2, the cleaning of waste and old Pilus Caprae seu Ovis and pulverizing；
Step 2.1, according to bath raio 1:30～50, weigh a certain amount of waste and old Pilus Caprae seu Ovis, 50～60 DEG C, pH value be under 8.5～9.5 conditions, the mixed solution being configured to the hydrogen peroxide 10～20ml/L of mass concentration 30%, sodium carbonate 0.5g/L～2g/L, sodium silicate 0.5g/L～2g/L processes 30～50min, then 10～20min is soaked with 30 DEG C～50 DEG C ethanol solutions, use rinsed with deionized water 1～3 time again, finally clean Pilus Caprae seu Ovis is dried under 80 DEG C～110 DEG C conditions.
Step 2.2, turn round the scoured wool that step 2.1 obtained of blade fibre cutting machine and cut into the length chopped fiber less than 5mm with rotating.
The preparation of nano-titanium dioxide powder in step 3, thermal and hydric environment；
Pilus Caprae seu Ovis chopped fiber is weighed according to the 1～10% of butyl titanate (or isopropyl titanate, titanium sulfate, titanium tetrachloride) consumption, and add it in the precursor solution that step 1 prepares, transfer them in high-temperature high-pressure reaction kettle after soaking 5～10min, mixed solution accounts for the 70%～90% of reactor volume, after sealing, high-temperature high-pressure reaction kettle is placed in homogeneous reactor, with 1 DEG C/min～3 DEG C/min ramp to 110 DEG C～130 DEG C, with 100～200 turns/min speed isothermal reaction 2h～5h.
After question response still is cooled to room temperature, the supernatant after centrifugal is outwelled, residual night is immersed in acetone soln, ultrasonic cleaning 10～20min when frequency 40kHz, power 100W, then ultrasonic cleaning 10～20min in ethanol solution it is immersed in, followed by deionized water ultrasonic cleaning 3 times, each 5～10min, last vacuum drying under 100 DEG C～120 DEG C conditions, grinds standby.
Embodiment 1
The butyl titanate measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stirs, and is then slowly added the deionized water of 70mL and stirs rapidly, and forming white " milky " clear solution hydrochloric acid conditioning solution pH value is 1.According to bath raio 1:30, weigh waste and old Pilus Caprae seu Ovis, 50 DEG C, pH value be under 8.5 conditions, the mixed solution being configured to the hydrogen peroxide 10ml/L of mass concentration 30%, sodium carbonate 0.5g/L, sodium silicate 0.5g/L processes 30min, then 10min is soaked with 30 DEG C of ethanol solutions, use rinsed with deionized water 1 time again, finally clean Pilus Caprae seu Ovis is dried under 80 DEG C of conditions.With rotating torsion blade fibre cutting machine, clean Pilus Caprae seu Ovis is cut into the length chopped fiber less than 5mm.Pilus Caprae seu Ovis chopped fiber is weighed according to the 1% of butyl titanate consumption, add it in precursor solution, transfer them in high-temperature high-pressure reaction kettle after soaking 5min, liquor capacity accounts for the 70% of reactor volume, after sealing, reactor is placed in homogeneous reactor and with 1 DEG C/min ramp to 110 DEG C, with 100 turns/min speed isothermal reaction 2h.After question response still is cooled to room temperature, the supernatant after centrifugal is outwelled, residual night is immersed in acetone soln, the ultrasonic cleaning 10min when frequency 40kHz, power 100W, is then immersed in ultrasonic cleaning 10min in ethanol solution, followed by deionized water ultrasonic cleaning 3 times, each 5min, last vacuum drying under 100 DEG C of conditions, after grinding, obtains nano-titanium dioxide powder.
Embodiment 2
The butyl titanate measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stirs, and is then slowly added the deionized water of 70mL and stirs rapidly, and forming white " milky " clear solution hydrochloric acid conditioning solution pH value is 2.According to bath raio 1:50, weigh a certain amount of waste and old Pilus Caprae seu Ovis, 60 DEG C, pH value be under 9.5 conditions, the mixed solution being configured to the hydrogen peroxide 20ml/L of mass concentration 30%, sodium carbonate 2g/L, sodium silicate 2g/L processes 50min, then 20min is soaked with 50 DEG C of ethanol solutions, use rinsed with deionized water 3 times again, finally clean Pilus Caprae seu Ovis is dried under 110 DEG C of conditions.With rotating torsion blade fibre cutting machine, clean Pilus Caprae seu Ovis is cut into the length chopped fiber less than 5mm.Pilus Caprae seu Ovis chopped fiber is weighed according to the 10% of butyl titanate consumption, add it in precursor solution, transfer them in high-temperature high-pressure reaction kettle after soaking 10min, liquor capacity accounts for the 90% of reactor volume, after sealing, reactor is placed in homogeneous reactor and with 3 DEG C/min ramp to 130 DEG C, with 200 turns/min speed isothermal reaction 5h.After question response still is cooled to room temperature, the supernatant after centrifugal is outwelled, residual night is immersed in acetone soln, the ultrasonic cleaning 20min when frequency 40kHz, power 100W, is then immersed in ultrasonic cleaning 20min in ethanol solution, followed by deionized water ultrasonic cleaning 3 times, each 10min, last vacuum drying under 120 DEG C of conditions, after grinding, obtains nano-titanium dioxide powder.
Embodiment 3
The butyl titanate measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stirs, and is then slowly added the deionized water of 70mL and stirs rapidly, and forming white " milky " clear solution hydrochloric acid conditioning solution pH value is 1.5.According to bath raio 1:40, weigh a certain amount of waste and old Pilus Caprae seu Ovis, 55 DEG C, pH value be under 9 conditions, the mixed solution being configured to the hydrogen peroxide 15ml/L of mass concentration 30%, sodium carbonate 1.5g/L, sodium silicate 1g/L processes 40min, then 15min is soaked with 40 DEG C of ethanol solutions, use rinsed with deionized water 2 times again, finally clean Pilus Caprae seu Ovis is dried under 100 DEG C of conditions.With rotating torsion blade fibre cutting machine, clean Pilus Caprae seu Ovis is cut into the length chopped fiber less than 5mm.Pilus Caprae seu Ovis chopped fiber is weighed according to the 6% of butyl titanate consumption, add it in precursor solution, transfer them in high-temperature high-pressure reaction kettle after soaking 8min, liquor capacity accounts for the 80% of reactor volume, after sealing, reactor is placed in homogeneous reactor and with 2 DEG C/min ramp to 120 DEG C, with 150 turns/min speed isothermal reaction 3h.After question response still is cooled to room temperature, the supernatant after centrifugal is outwelled, residual night is immersed in acetone soln, the ultrasonic cleaning 15min when frequency 40kHz, power 100W, is then immersed in ultrasonic cleaning 15min in ethanol solution, followed by deionized water ultrasonic cleaning 2 times, each 7min, last vacuum drying under 110 DEG C of conditions, after grinding, obtains nano-titanium dioxide powder.
Embodiment 4
The titanium tetrachloride measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stirs, and is then slowly added the deionized water of 70mL and stirs rapidly, and forming white " milky " clear solution hydrochloric acid conditioning solution pH value is 1.According to bath raio 1:35, weigh waste and old Pilus Caprae seu Ovis, 50 DEG C, pH value be under 8.5 conditions, the mixed solution being configured to the hydrogen peroxide 10ml/L of mass concentration 30%, sodium carbonate 0.8g/L, sodium silicate 0.8g/L processes 35min, then 10min is soaked with 30 DEG C of ethanol solutions, use rinsed with deionized water 1 time again, finally clean Pilus Caprae seu Ovis is dried under 90 DEG C of conditions.With rotating torsion blade fibre cutting machine, clean Pilus Caprae seu Ovis is cut into the length chopped fiber less than 5mm.Pilus Caprae seu Ovis chopped fiber is weighed according to the 1% of titanium tetrachloride consumption, add it in precursor solution, transfer them in high-temperature high-pressure reaction kettle after soaking 6min, liquor capacity accounts for the 70% of reactor volume, after sealing, reactor is placed in homogeneous reactor and with 1 DEG C/min ramp to 115 DEG C, with 130 turns/min speed isothermal reaction 3h.After question response still is cooled to room temperature, the supernatant after centrifugal is outwelled, residual night is immersed in acetone soln, the ultrasonic cleaning 12min when frequency 40kHz, power 100W, is then immersed in ultrasonic cleaning 12min in ethanol solution, followed by deionized water ultrasonic cleaning 3 times, each 8min, last vacuum drying under 100 DEG C of conditions, after grinding, obtains nano-titanium dioxide powder.
Embodiment 5
The titanium tetrachloride measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stirs, and is then slowly added the deionized water of 70mL and stirs rapidly, and forming white " milky " clear solution hydrochloric acid conditioning solution pH value is 2.According to bath raio 1:48, weigh a certain amount of waste and old Pilus Caprae seu Ovis, 60 DEG C, pH value be under 9.5 conditions, the mixed solution being configured to the hydrogen peroxide 20ml/L of mass concentration 30%, sodium carbonate 2g/L, sodium silicate 2g/L processes 50min, then 20min is soaked with 50 DEG C of ethanol solutions, use rinsed with deionized water 3 times again, finally clean Pilus Caprae seu Ovis is dried under 105 DEG C of conditions.With rotating torsion blade fibre cutting machine, clean Pilus Caprae seu Ovis is cut into the length chopped fiber less than 5mm.Pilus Caprae seu Ovis chopped fiber is weighed according to the 10% of titanium tetrachloride consumption, add it in precursor solution, transfer them in high-temperature high-pressure reaction kettle after soaking 10min, liquor capacity accounts for the 90% of reactor volume, after sealing, reactor is placed in homogeneous reactor and with 3 DEG C/min ramp to 125 DEG C, with 190 turns/min speed isothermal reaction 5h.After question response still is cooled to room temperature, the supernatant after centrifugal is outwelled, residual night is immersed in acetone soln, the ultrasonic cleaning 20min when frequency 40kHz, power 100W, then ultrasonic cleaning 20min in ethanol solution it is immersed in, followed by deionized water ultrasonic cleaning 3 times, each 10min, last vacuum drying under 120 DEG C of conditions, grinds standby.
Embodiment 6
The titanium tetrachloride measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stirs, and is then slowly added the deionized water of 70mL and stirs rapidly, and forming white " milky " clear solution hydrochloric acid conditioning solution pH value is 1.5.According to bath raio 1:38, weigh a certain amount of waste and old Pilus Caprae seu Ovis, 56 DEG C, pH value be under 9 conditions, the mixed solution being configured to the hydrogen peroxide 16ml/L of mass concentration 30%, sodium carbonate 1.5g/L, sodium silicate 1g/L processes 40min, then 15min is soaked with 40 DEG C of ethanol solutions, use rinsed with deionized water 2 times again, finally clean Pilus Caprae seu Ovis is dried under 100 DEG C of conditions.With rotating torsion blade fibre cutting machine, clean Pilus Caprae seu Ovis is cut into the length chopped fiber less than 5mm.Pilus Caprae seu Ovis chopped fiber is weighed according to the 5% of titanium tetrachloride consumption, add it in precursor solution, transfer them in high-temperature high-pressure reaction kettle after soaking 7min, liquor capacity accounts for the 80% of reactor volume, after sealing, reactor is placed in homogeneous reactor and with 2 DEG C/min ramp to 120 DEG C, with 150 turns/min speed isothermal reaction 3h.After question response still is cooled to room temperature, the supernatant after centrifugal is outwelled, residual night is immersed in acetone soln, the ultrasonic cleaning 15min when frequency 40kHz, power 100W, is then immersed in ultrasonic cleaning 15min in ethanol solution, followed by deionized water ultrasonic cleaning 2 times, each 7min, last vacuum drying under 110 DEG C of conditions, after grinding, obtains nano-titanium dioxide powder.
Embodiment 7
The isopropyl titanate measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stirs, and is then slowly added the deionized water of 70mL and stirs rapidly, and forming white " milky " clear solution hydrochloric acid conditioning solution pH value is 1.5.According to bath raio 1:45, weigh a certain amount of waste and old Pilus Caprae seu Ovis, 53 DEG C, pH value be under 9 conditions, the mixed solution being configured to the hydrogen peroxide 16ml/L of mass concentration 30%, sodium carbonate 1.5g/L, sodium silicate 1.3g/L processes 40min, then 15min is soaked with 40 DEG C of ethanol solutions, use rinsed with deionized water 2 times again, finally clean Pilus Caprae seu Ovis is dried under 90 DEG C of conditions.With rotating torsion blade fibre cutting machine, clean Pilus Caprae seu Ovis is cut into the length chopped fiber less than 5mm.Pilus Caprae seu Ovis chopped fiber is weighed according to the 7% of isopropyl titanate consumption, add it in precursor solution, transfer them in high-temperature high-pressure reaction kettle after soaking 8min, liquor capacity accounts for the 80% of reactor volume, after sealing, reactor is placed in homogeneous reactor and with 2 DEG C/min ramp to 120 DEG C, with 150 turns/min speed isothermal reaction 3.5h.After question response still is cooled to room temperature, the supernatant after centrifugal is outwelled, residual night is immersed in acetone soln, the ultrasonic cleaning 15min when frequency 40kHz, power 100W, is then immersed in ultrasonic cleaning 15min in ethanol solution, followed by deionized water ultrasonic cleaning 2 times, each 7min, last vacuum drying under 110 DEG C of conditions, after grinding, obtains nano-titanium dioxide powder.
Embodiment 8
The carbamide of the titanium sulfate and 10g that measure 4g is dissolved in the ethanol solution of 5mL, and constantly stirs, and is then slowly added the deionized water of 70mL and stirs rapidly, and forming white " milky " clear solution hydrochloric acid conditioning solution pH value is 1.5.According to bath raio 1:38, weigh a certain amount of waste and old Pilus Caprae seu Ovis, 57 DEG C, pH value be under 9 conditions, the mixed solution being configured to the hydrogen peroxide 15ml/L of mass concentration 30%, sodium carbonate 1.5g/L, sodium silicate 1g/L processes 40min, then 15min is soaked with 40 DEG C of ethanol solutions, use rinsed with deionized water 3 times again, finally clean Pilus Caprae seu Ovis is dried under 95 DEG C of conditions.With rotating torsion blade fibre cutting machine, clean Pilus Caprae seu Ovis is cut into the length chopped fiber less than 5mm.Pilus Caprae seu Ovis chopped fiber is weighed according to the 8% of titanium sulfate consumption, add it in precursor solution, transfer them in high-temperature high-pressure reaction kettle after soaking 9min, liquor capacity accounts for the 80% of reactor volume, after sealing, reactor is placed in homogeneous reactor and with 2 DEG C/min ramp to 130 DEG C, with 180 turns/min speed isothermal reaction 2.5h.After question response still is cooled to room temperature, the supernatant after centrifugal is outwelled, residual night is immersed in acetone soln, the ultrasonic cleaning 15min when frequency 40kHz, power 100W, is then immersed in ultrasonic cleaning 15min in ethanol solution, followed by deionized water ultrasonic cleaning 2 times, each 8min, last vacuum drying under 110 DEG C of conditions, after grinding, obtains nano-titanium dioxide powder.
Comparative example 1
The butyl titanate measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stirs, and is then slowly added the deionized water of 70mL and stirs rapidly, and forming white " milky " clear solution hydrochloric acid conditioning solution pH value is the precursor solution of 1.5.Being transferred in high-temperature high-pressure reaction kettle by precursor solution, liquor capacity accounts for the 80% of reactor volume, is placed in homogeneous reactor by reactor and with 2 DEG C/min ramp to 120 DEG C after sealing, with 150 turns/min speed isothermal reaction 3h.After question response still is cooled to room temperature, the supernatant after centrifugal is outwelled, residual night is immersed in acetone soln, the ultrasonic cleaning 15min when frequency 40kHz, power 100W, is then immersed in ultrasonic cleaning 15min in ethanol solution, followed by deionized water ultrasonic cleaning 2 times, each 7min, last vacuum drying under 110 DEG C of conditions, after grinding, obtains nano-titanium dioxide powder.
Comparative example 2
The titanium tetrachloride measuring 5mL is dissolved in the ethanol solution of 5mL, and constantly stirs, and is then slowly added the deionized water of 70mL and stirs rapidly, and forming white " milky " clear solution hydrochloric acid conditioning solution pH value is the precursor solution of 1.5.Being transferred in high-temperature high-pressure reaction kettle by precursor solution, liquor capacity accounts for the 80% of reactor volume, is placed in homogeneous reactor by reactor and with 2 DEG C/min ramp to 120 DEG C after sealing, with 150 turns/min speed isothermal reaction 3h.After question response still is cooled to room temperature, the supernatant after centrifugal is outwelled, residual night is immersed in acetone soln, the ultrasonic cleaning 15min when frequency 40kHz, power 100W, is then immersed in ultrasonic cleaning 15min in ethanol solution, followed by deionized water ultrasonic cleaning 2 times, each 7min, last vacuum drying under 110 DEG C of conditions, after grinding, obtains nano-titanium dioxide powder.
Nano titanium dioxide photocatalysis rhodamine B degradation dyestuff performance test of the present invention adopts photochemical reaction instrument, detailed process is: diameter be about in the quartz glass test tube of 2cm add volume 50mL, mass percent concentration 5mg/L rhodamine B solution, add the nano-titanium dioxide powder of 0.01g again and put into magnetic rotor, it is placed in darkroom magnetic agitation 60min, will be equipped with the test tube of rhodamine B solution after reaching adsorption equilibrium be positioned in photochemical reaction instrument and carry out irradiation with the mercury lamp of 1000W, test tube is from light source 15cm.Measure photocatalytic activity during ultraviolet irradiation with below 400nm optical filter, take out the solution spectrophotometer of certain volume every 10min and measure absorbance at 554nm place.Measure photocatalytic activity during visible light exposure with 400nm with upper filter, take out the solution spectrophotometer of certain volume every 15min and measure absorbance at 554nm place.And the degradation rate D of rhdamine B is calculated according to formula (1).
In formula: C0It is the initial concentration adsorbing saturated rear rhodamine B solution, CtBeing the concentration of rhodamine B solution after irradiation certain time, t is exposure time.
Test result is: the embodiment of the present invention 1 gained nano titanium oxide degradation rate after ultraviolet irradiation 60min is 94%, it is seen that after photoirradiation 90min, degradation rate is 92%.The embodiment of the present invention 2 gained nano titanium oxide degradation rate after ultraviolet irradiation 60min is 95%, it is seen that after photoirradiation 90min, degradation rate is 94%.The embodiment of the present invention 3 gained nano titanium oxide degradation rate after ultraviolet irradiation 60min is 99%, it is seen that after photoirradiation 90min, degradation rate is 98%.
Fig. 1 is the stereoscan photograph of the embodiment of the present invention 3 gained nano titanium oxide.It can be seen that adding the titanium dioxide that chippy wool fiber butyl titanate prepares is nanoscale, particle size size ratio is more uniform.Fig. 2 is the stereoscan photograph of the embodiment of the present invention 6 gained nano titanium oxide.It can be seen that adding the titanium dioxide that chippy wool fiber titanium tetrachloride prepares is nanoscale, particle size is relatively.Fig. 3 is the energy spectrogram of the embodiment of the present invention 3 gained nano titanium oxide.It can be seen that butyl titanate adds containing a certain amount of organic principle in the nano titanium oxide that Pilus Caprae seu Ovis is prepared, except O, Ti element, possibly together with C, N, S and Cl element.Fig. 4 is the energy spectrogram of the embodiment of the present invention 6 gained nano titanium oxide.It can be seen that titanium tetrachloride adds containing a certain amount of organic principle in the nano titanium oxide that Pilus Caprae seu Ovis is prepared, except O, Ti element, possibly together with C, S and Cl element.Fig. 5 is the X-ray diffraction spectrogram of embodiment 3, embodiment 6, comparative example 1 and comparative example 2 gained nano titanium oxide.Can be seen that, using the nano titanium oxide that butyl titanate (comparative example 1) is prepared is 25.3 ° in the angle of diffraction, 37.8 °, 48.0 °, 55.1 °, 62.7 °, 68.8 ° and 75.0 ° of places occur in that obvious diffraction maximum, for Detitanium-ore-type, and butyl titanate adds the nano titanium oxide that Pilus Caprae seu Ovis (embodiment 3) prepares and also occurs in that diffraction maximum in same position, but intensity reduces to some extent, it was shown that particle size is less.Using the nano-titanium dioxide powder that titanium tetrachloride (comparative example 2) is prepared is 27.5 ° in the angle of diffraction, 36.1 °, 41.3 °, 54.4 °, 62.8 °, 69.1 ° of places occur in that stronger diffraction maximum, for rutile-type, and titanium tetrachloride adds the nano titanium oxide that Pilus Caprae seu Ovis (embodiment 6) prepares and also occurs in that diffraction maximum in same position, intensity reduces to some extent and shows that particle size reduces to some extent.Fig. 6 is the UV-Vis reflective spectrum curve of embodiment 3, embodiment 6, comparative example 1 and comparative example 2 gained nano titanium oxide.Compared with the nano titanium oxide that titanium tetrachloride (comparative example 2) is prepared, titanium tetrachloride adds the nano titanium oxide that Pilus Caprae seu Ovis (embodiment 6) prepares and the absorption of ultraviolet and visible ray is obviously enhanced.The nano titanium oxide that relatively butyl titanate (comparative example 1) is prepared, butyl titanate adds the nano titanium oxide that Pilus Caprae seu Ovis (embodiment 3) prepares and the absorbability of ultraviolet and visible ray is also remarkably reinforced, it is meant that add the photo-catalytic activity of nano titanium dioxide that Pilus Caprae seu Ovis prepares higher.Fig. 7 is the ultraviolet irradiation photocatalytic degradation rhodamine B curve of embodiment 3, embodiment 6, comparative example 1 and comparative example 2 gained nano titanium oxide.It can be seen that during ultraviolet irradiation photocatalytic degradation rhodamine B, butyl titanate adds the photo-catalytic activity of nano titanium dioxide that Pilus Caprae seu Ovis (embodiment 3) prepares and is better than the nano titanium oxide that butyl titanate (comparative example 1) is prepared；Titanium tetrachloride adds the photo-catalytic activity of nano titanium dioxide that Pilus Caprae seu Ovis (embodiment 6) prepares and is also better than the nano titanium oxide that titanium tetrachloride (comparative example 2) is prepared.Fig. 8 is the visible light exposure photocatalytic degradation rhodamine B curve of embodiment 3, embodiment 6, comparative example 1 and comparative example 2 gained nano titanium oxide.It can be seen that during visible light exposure photocatalytic degradation rhodamine B, butyl titanate adds the photo-catalytic activity of nano titanium dioxide that Pilus Caprae seu Ovis (embodiment 3) prepares and is better than the nano titanium oxide that butyl titanate (comparative example 1) is prepared；Titanium tetrachloride adds the photo-catalytic activity of nano titanium dioxide that Pilus Caprae seu Ovis (embodiment 6) prepares and is equally also better than the nano titanium oxide that titanium tetrachloride (comparative example 2) is prepared.
Claims (9)
1. one kind utilizes the method that waste and old Pilus Caprae seu Ovis prepares highlight catalytic active nano titanium dioxide, it is characterised in that concrete preparation process is:
Step 1, utilizes titanium salt to prepare precursor solution；
Step 2, waste and old Pilus Caprae seu Ovis pretreatment, obtain Pilus Caprae seu Ovis chopped fiber；
Step 3, utilizes the precursor solution of step 1 gained and step 2 gained Pilus Caprae seu Ovis chopped fiber to carry out the preparation of nano-titanium dioxide powder.
2. a kind of method utilizing waste and old Pilus Caprae seu Ovis to prepare highlight catalytic active nano titanium dioxide according to claim 1, it is characterised in that in step 1, the process for preparation of precursor solution is:
Weighing titanium salt, be dissolved in dehydrated alcohol, after stirring, be slowly added to deionized water, obtain white " milky " clear solution, recycling hydrochloric acid or sulphuric acid regulate its pH to 1～2, obtain precursor solution, standby.
3. a kind of method utilizing waste and old Pilus Caprae seu Ovis to prepare highlight catalytic active nano titanium dioxide according to claim 2, it is characterised in that described titanium salt is the one in butyl titanate, isopropyl titanate, titanium sulfate or titanium tetrachloride.
4. a kind of method utilizing waste and old Pilus Caprae seu Ovis to prepare highlight catalytic active nano titanium dioxide according to claim 3, it is characterised in that in gained precursor solution, titanium salt is 1:1 with the amount ratio of dehydrated alcohol；The consumption of deionized water is 7 times of titanium salt and dehydrated alcohol total amount.
5. a kind of method utilizing waste and old Pilus Caprae seu Ovis to prepare highlight catalytic active nano titanium dioxide according to claim 1, it is characterised in that in step 2, the detailed process of Pilus Caprae seu Ovis pretreatment is:
Step 2.1: weigh waste and old Pilus Caprae seu Ovis, it is placed in alkaline mixed solution immersion treatment 30～50min, then soak 10～20min with 30 DEG C～50 DEG C ethanol solutions, then by rinsed with deionized water 1～3 time, finally clean Pilus Caprae seu Ovis is dried under 80 DEG C～110 DEG C conditions；
Step 2.2: step 1.1 gained Pilus Caprae seu Ovis is cut into the length chopped fiber less than 5mm with rotating torsion blade fibre cutting machine.
6. a kind of method utilizing waste and old Pilus Caprae seu Ovis to prepare highlight catalytic active nano titanium dioxide according to claim 5, it is characterized in that, in step 2.1, the pH of alkaline mixed solution is 8.5～9.5, alkaline mixed solution is mixed by hydrogen peroxide, sodium carbonate and sodium silicate, wherein, the hydrogen peroxide 10～20ml/L of mass concentration 30%, sodium carbonate 0.5g/L～2g/L, sodium silicate 0.5g/L～2g/L.
7. the bath raio of a kind of method utilizing waste and old Pilus Caprae seu Ovis to prepare highlight catalytic active nano titanium dioxide according to claim 6, it is characterised in that in step 2.1, waste and old Pilus Caprae seu Ovis and alkaline mixed solution is 1:30～50.
8. a kind of method utilizing waste and old Pilus Caprae seu Ovis to prepare highlight catalytic active nano titanium dioxide according to claim 1, it is characterised in that in step 3, the concrete preparation process of nano-titanium dioxide powder is:
Step 3.1: step 1 gained Pilus Caprae seu Ovis chopped fiber is immersed in step 2 gained precursor solution after 5～10min, it is transferred in high-temperature high-pressure reaction kettle, after sealing, high-temperature high-pressure reaction kettle is placed in homogeneous reactor, with 1 DEG C/min～3 DEG C/min ramp to 110 DEG C～130 DEG C, after 100～200 turns/min speed isothermal reaction 2h～5h, it is cooled to room temperature, is centrifuged processing；
Step 3.2: the supernatant after centrifugal is outwelled, residual liquid is immersed in acetone soln, ultrasonic cleaning 10～20min when frequency 40kHz, power 100W, then ultrasonic cleaning 10～20min in ethanol solution it is immersed in, followed by deionized water ultrasonic cleaning 3 times, each 5～10min, finally vacuum drying under 100 DEG C～120 DEG C conditions, after grinding, obtain nano-titanium dioxide powder.
9. a kind of method utilizing waste and old Pilus Caprae seu Ovis to prepare highlight catalytic active nano titanium dioxide according to claim 8, it is characterised in that in step 3.1, the consumption of Pilus Caprae seu Ovis chopped fiber is in precursor solution the 1～10% of titanium salt consumption.
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